High molecular weight halogenated materials stabilized with a mixture of an epoxy compound and a carboxylic acid salt



Patented Mar. 18, 1952 HIGH MOLECULAR WEIGHT HALOGENATED MATERIALSSTABILIZED WITH A MIX- TURE OF AN EPOXY COMPOUND AND A CARBOXYLIC ACIDSALT De Loss E1 Winkler, Berkeley, Calif., assignor to Shell DevelopmentCompany, San Francisco, Calif., a corporation of Delaware No Drawing.Application March 26, 1949,

Serial No. 83,776

9 Claims. (Cl. 260-4575) This invention relates to a new composition ofmatter containing a high molecular weight halogenated organic materialand a stabilizer therefor which inhibits or prevents the deterioratingeffects of heat and light. More particularly, the invention is concernedwith a composition containing a polymer of vinyl chloride in admixturewith an especially efiective stabilizer Halogen-containing organicmaterials of high molecular weight such as polymers and copolymers ofvinyl chloride are usually fabricated into useful articles by use ofheat in milling and/or molding operations. However, these fabricatingoperations employing heat tend to decompose the halogen-containingmaterial so that it becomes discolored as well as stiifens and losespliability. Moreover, exposure of the halogen-containing material tolight, especially sunlight which is rich in ultraviolet radiation, alsocauses discoloration as well as softening of the halogen containingmaterial. Various substances have been added to retard or prevent suchdiscoloration and deterioration, but the need for improvement in thisrespect still re mains.

Among various substances used as stabilizers for polymers of vinylchloride are strontium or cadmium salts of carboxylic acids. Moreover,as described and claimed in copending application, Serial No. 774,660,filed September 17, 1947, now abandoned, halogen-containing organicmaterials may be stabilized by incorporation therewith of etherscontaining a plurality of epoxyalkoxy radicals, e. g., ethers containinga plurality of glycidyl groups. While use of either the metal salt aloneor the epoxy compound alone has a stabilizing effect, it has now beendiscovered quite unexpectedly that incorporation of both an epoxycompound along with a strontium or cadmium carboxylic acid salt producesa synergistic stabilizing efiect. In other words, the stabilizing effectproduced by use of the two different substances 'in combinationisconsiderably greater than the. sum of the stabilizing eifects expectedfrom use of either substances alone. p

' Accordingly, the principal aspect of the invention is directed to thenew composition of matter containing a halogen-containing organicmaterial of molecular weightabove 2000'having incorporated or admixedtherewith a stabilizer consisting essentially of (1) a glycidyl etherhaving a 1,2-epoxy equivalency greater than one and (2) a carboxylicacid salt of strontium or cadmium. Such compositions have superiorresistance against the deteriorating eifects of heat and; light than ispossible, with use of either the '2 glycidyl ether alone or the metalsalt alone even though the proportions are the same as the total of thetwo substances in the composition.

The high molecular weight halogen-containing material which is theprincipal constituent of the composition may be any substance containingan appreciable proportion of halogen and a molecular weight of at least2000. No particular upper limit to the molecular weight is necessary torealize the advantages of the invention so long as it is above 2000. Thestabilization is obtained with the halogen-containing organic materialshaving molecular weights of about 50,000, 100,000, 150,000 or higher.While it is preferred to employ the principle of the invention for-thepurpose of stabilizing chlorinecontaining organic materials, substancescontaining other halogens such as bromine, fluorine or iodine are alsosuitable. In general, the halogen atom or atoms are linked directly to acarbon atom which in turn is linked to no other atoms than carbon,hydrogen or other halogen atoms which may be the same or diiferent fromthe first. Among the materials stabilized, are polyvinyl chloride,after-chlorinated polyvinyl chloride,- copolymers of vinyl chloride withvarious polymerizable compounds containing olefinic double bonds such asvinyl acetate, vinyl chloride, acrylonitrile, maleic anhydride, styrene,etc.; halogenated polyolefins such as chlorinated polyethylene,brominated polyisobutylene, etc.; polymers of chloroprene as well ascopolymers thereof with other polymerizable unsaturated compounds suchas those named above; halogenated products of fats, train oils, waxes,and the high-boiling hydrocarbons and the like. In general, thestabilizing influence is particularly suitable with substancescontaining at least 10% halogen, particularly those with up to halogen.Excellent results have been obtained upon stabilizing polyvinyl chlorideas well as copolymers of vinyl chloride with up to 15% vinyl acetate.

The glycidyl ethers suitable for use in the composition contain at least6 carbon atoms as well as one or more ethereal oxygen atoms andpreferably have a boilin point above 300 C. By the epoxy equivalencyreference is made to the number of 1,2-epoxy groups cmcH- contained inthe average molecule of the ether. In the case wherein a substantiallypure, simple compound is used, the epoxy equivalency will be an integerof two or more. For example, the epoxy equivalency of such suitablecompounds as diglycidyl ether or the diglycidyl ether of ethylene glycolis two while that of the triglycidyl ether of glycerol is three.However, the glycidyl ether may be a mixture of chemical compounds whichalthough they are of similar identity and chemical constitution havedifferent molecular weights The measured molecular weight of themixtureupon which the epoxy equivalency is dependent will necessarily bean average molecular weight. Consequently, the epoxy equivalency of theglycidyl ether mixture will not necessarily be an integer'butnevertheless will be a value which is greather than one. For example, aglycidyl ether suitable for use in the invention is that'made byreacting bis-(4-hydroxyphenyl)-2,2-propane with epichlorhydrin inalkaline solution at a mole ratio of about 2.0 moles of epichlorhydrinper mole of the dihydric phenol. The product is a resinous mixture ofglycidyl ethers having a measured average molecular weight of 451.Analysis shows the product to contain about 0.318 equivalents of epoxygroups per 100 grams. Consequently, the product has a 1,2-epoxyequivalency of about 1.39, i.'e., an average of about 1.39 epoxygroups'per molecule.

The glycidyl ethers used to'stabilize the composition preferably containonly the elements carbon, hydrogen and oxygen. They include 1,2-epoxy-containing polyethers of polyhydric alcohols such as polyglycidylethers thereof like the diglycidyl ether of ethylene glycol, propyleneglycol, trimethylene glycol, butylene glycol, glycerol, and the like.Other typical ethers of this class include glycidyl ethers of polyhydricalcohols having a 1,2-epoxy equivalency greater than one such as thepolyglycidyl ethers of glycerol, diglycerol, erythritol, pentaglycerol,pentaerythritol, mannitol, sorbitol, polyallyl alcohol, polyvinylalcohol and the like. The polyglycidyl ethers of the polyhydric alcoholsare prepared by reacting the polyhydric alcohol with epichlorhydrin inthe presence of 0.1 to 2% of an acid-acting compound as catalyst such asboron 'trifiuoride, hydrofluoric acid or stannic chloride whereby thechlorhydrin ether is formed as product. The reaction is effected atabout 50 to 125 C. with the proportions of reaction being suchthat thereis about 1 mole of epichlorhydrin for each molecular equivalent ofhydroxyl group in the polyhydric alcohol. Thus, in preparing theether ofdiethylene glycol which-glycol contains two hydroxyl groups in eachmolecule thereof, about two moles of epichlorhydrin for each mole ofdiethylene glycol are used. The resulting chlorhydrin ether from thereaction of a polyhydric alcohol with epichlorhydrin isdehydrochlorinated by heating at about 50 C. to 125 C. with a small, saystoichiometrical excess of a base. For this purpose sodium aluminategives good results.

Preparation of several glycidyl ethers of polyhydric alcohols suitablefor use as stabilizer in the composition of the invention areillustrated in the following examples.

Example I In a reaction vesselprovided with a mechanical stirrer andexternal cooling means was placed a quantity of 276 parts of glyceroland 828 parts of epichlorhydrin, and to this reaction mixture was addedone part of boron trifluoride ether solution diluted with nine'parts ofether. The reaction mixture was agitated continuously, the

temperature rising to C. during a period. of

one hour and 44 minutes, at which time external cooling with ice waterwas applied. Thetemperature of the reaction mixture was maintainedbetween 49 C. and 77 C. for one hour and 21 minutes.

To 370 parts of the product formed from glycerol and epichlorhydrin wasadded 900 parts of dioxane and 300 parts of powdered sodium aluminate(Na'2A1204), in a reaction vessel provided with a mechanical agitatorand a reflux condenser. The reaction mixture thus formed wascontinuously agitated and gradually heated to 93 C. during a period ofone hour and 51 minutes. The temperature was held at 93 C. for a periodof eight hours and 49 minutes. The reaction mixture was then cooled toroom temperature (20-25 C.) and this inorganic material, such as sodiumchloride and aluminum oxide, was removed by filtration of the cooledmixture. 'Dioxane and low boiling products were removed by heating thefiltrate to 205 C. at 20 mm. pressure,

whereupon 261 parts of a pale yellow product was obtained as a residue.This product had a viscosity of D-E (Gardner-Holdt scale) and,therefore, a softening point (Durrans Mercury Method) substantiallybelow 20 C. The product had an equivalent weight to epoxide of 149.

Example II In a reaction vessel fitted with a thermometer, refluxcondenser, gas inlet tube and electrically- V driven stirrer, wereplaced 272 grams of powdered mixture was heated at -130 C. for 50minutes. Ethylene oxide was then introduced through the gas inlet tube,for 3 hours at 125-170 C. The total quantity of ethylene oxide sointroduced was 202 grams (4.6 moles).

The'resulting'reaction mixture was transferred to a reaction vessel,fitted with thermometer, reflux condenser and electrically-drivenstirrer and heated to 120 C. Six cc. of the BFs-ethyl ether solutionwere added. Epichlorhydrin (1570 grams; 17 moles) was then added duringa period of 2 hours and 25 minutes, during which period the temperaturevaried from 97 C. to 118 C.

A quantity, 231 grams, of the epichlorhydrin reaction product soobtained was placed in a reaction vessel equipped with a'thermometer,reflux condenser and electrically-driven stirrer. Three hundred cc. ofdioxane, 20 cc. of water and grams of sodium aluminate (Na2Al2O4) wereadded. The reaction mixture thus-formed was continuously agitated andheated at about 96 C. for 3 hours. The reaction mixture was treated asdescribed in Example 1 above, except that-the vacuum distillation wascontinued to 200 C. at 3 mm. pressure. The product, 159 grams, was aclear, very pale yellow liquid, having a viscosity of H (Gardner-Holdtscale). The product also had an epoxide equivalent to 161 and an averagemolecular weight of 360 (determined by standard freezing point methodwith benzophenone) this corresponds to an average of about 2.2 epoxidegroups per molecule.

The 1,2-epoxide value of the glycidyl ethers described herein isdetermined by heating a one .gram sample of the ether with an excess ofthe pyridinium chloride dissolved in pyridine (made drochloric acid to atotal volume of 1 liter) at the boiling point for 20 minutes whereby thepyridinium chloride hydrochlorinates the epoxy groups to chlorhydringroups. The excess pyridinium chloride isthen back titrated with 0.1 Nsodium hydroxide to the phenolphthalein end point. The epoxide value iscalculated by considering the HCl as equivalent to the epoxide group.This method is used for obtaining all the epoxide values discussedherein.

A preferred group of glycidyl ethers for use as stabilizer in thecomposition of the invention is the ether prepared by reacting adihydric phenol with epichlorhydrin in alkaline solution. Any of thevarious dihydric phenols are used in preparing these glycidyl ethersincluding mononuclear phenols like resorcinol, catechol, hydroquinone,etc., or polynuclear phenols like his (4 hydroxyphenyl) 2,2propane(bisphenol), 4,4'-dihydroxy, benzophenone, bis-(4- hydroxyphenyl)1,1 ethane, bis-( l-hydroxyphenyl) 1,1 isobutane, bis-(4-hydroxyphenyD-2,2butane, bis-(4 hydroxy 2-methylphenyl)- 2,2 -propane,"bis-(4-hydroxy-2-tertiary butyl phenyl) -2,2 propane, bis-(-dihydroxy-naphthyl)-methane, 1,5-dihydroxy naphthalene, etc.

The glycidyl ethers of the dihydric phenols are made by heating at 50 C;to 150 C. the

dihydric phenol with epichlorhydrin, using one to two or more moles ofepichlorhydrin per mole of the dihydric phenol. Also present is a basesuch as sodium, potassium, calcium or barium hydroxide in amount of to30% stoichiometric excess of the epichlorhydrin i. e., 1.1 to 1.3equivalents of base per mole of epichlorhydrin. The heating is continuedfor several hours to convert the reaction mixture to a taffy-likeconsistency whereupon the reaction product is washed with water untilfree of base. Although the product is a complex mixture of glycidylethers, the principal product may be represented by the formula Thecooled reaction mixture was freed of precipitated sodium chloride, andthe organic portion fractionally distilled. A yield of 0.7 moles (70%)of resorcinyl bisglycidyl ether was obtained in the form of a colorless,bright and viscous liquid, which after being left undisturbed for sometime at room temperature slowly crystallized. The ether was readilysoluble in various organic solvents, but practically insoluble in water,and had a melting point of from 33- 36 C. and a boiling range of from142-152 C. at 0.04 mm.

Example IV A solution consisting of 11.7 pounds E20, 1.22 pounds NaOHand 13.38 pounds of bisphenol was prepared by heating to 70 C., and thencooling to 46 C. at which temperature 14.06 pounds of epichlorhydrinwere added. The addition of cold caustic solution (5.62 pounds NaOH in11.7 pounds H2O) was started minutes later; the solution was added overa period of 15 minutes, during which time the temperature rose to 63 C.The maximum temperature reached was 71 C. Washing was started minutesafter addition of the NaOH solution, and was continued for 4 /2 hours,the temperature of the wash water being increased from 20 C. at thebeginning to 30 C. at the end. It was dried (with steam heating) to afinal temperature of 140 C. in 80 minutes, and cooled rapidly. Thisproduct had a Durrans Mercury melting point of 27 C. and an epoxideequivalent weight of 249.

Example V wherein R represents the divalent hydrocarbon radical of thedihydric phenol and n is 0, 1, 2, 3, etc. The length of the chain can bemade to vary :by changing the molecular proportion of epichlorhydrin anddihydric phenol. Thus by decreasing the moles of epichlorhydrin per moleof dihydric alcohol from about two downwards toward'one, the molecularweight and the softening point of the resinous glycidyl ether isincreased. In general, these glycidyl ethers, having an epoxyequivalency between one and two, contain terminal 1,2-epoxy groups, andhave alternate aliphatic and aromatic groups linked together by etherealoxygen atoms.

The preparation of glycidyl ethers of polyhydric phenols suitable foruse in the invention are illustrated by the examples below.

Example III in amount of 650 parts was added in one portion to theclosed kettle. The kettle was provided with a stirrer and the mixturewas stirred during the process. The temperature rose from about 37 C. toabout C. in 45 minutes. Caustic soda, parts in 200 parts of water, wasthen added, whereupon the temperature rose to about 82 C. during thecourse of a further 30 minutes. Additional caustic soda, 29 parts inparts of water, was then added and the kettle was heated. Thetemperature of the reaction mixture was gradually increased to about 95C. in approximately 30 minutes. The aqueous liquor was next drawn offfrom the taiiy-like product which" had formed. The latter was washedwith hot water while agitated and a series of washing treatments wereapplied until the water was neutral to litmus. The product was thendried by heating to a final temperature of C. and removed from thekettle. The softening point of the resulting glycidyl ether by DurransMercury Method was 43 C. The epoxide equivalent weight was 325.

The other component of the stabilizer is a cadmium or strontium salt ofa carboxylic acid. Whileit is preferred to employ a salt of amonocarboxylic acid of 12 to 20 carbon atoms containingno more than oneolefinic double bond 7 therein, salts of other acids may be used ifdesired such as asalt of acetic, hexanoic, octanoic, lauric, palmitic,or stearic acid; a salt of crotonic or oleicacid; a salt of linoleicorlinolenic acid;

a salt of benzoic or toluic acid; a salt of a polycarboxylic acid likephthalic, adipic, or maleic acid, a salt of a substituted acid such aschlorostearic, bromopalmitic, salicylic, anthranilic or tryptophan acid;and the like. The salt may thus be of any carboxylic acid substituted orunsubstituted, monobasic or polybasic, since it is the metal part of thesalt which is efiective in producing the desired stabilizing efiect.Nevertheless, certain classes of salts are more preferred than others,namely, those of saturated monocarboxylic acids of 12 to 20 carbonatoms. For this purpose, strontium or cadmium salts of sat urated fattyacids are well suited, as well as salts of naphthenic acids,particularly those 'havin an acid number of about 180 to 280, especially200 to 220.

The valuable synergistic stabilizing efiect obtained with thecombination of substances employed in the compositions of the inventionwill be evident upon consideration of the data given in Table I below.

Table I gives the extinction coeflicients obtained with compositionscontaining polyvinyl chloride having a molecular weight of about 100,-

000 and various stabilizers and combinations thereof before and afterheat treatment. Of the stabilizers, Epoxy IV designates the glycidylether prepared as described in Example IV above; Cd Naph. representscadmium naphthenate, "Sr stearate represents strontium stearate and SrNaph. represents strontium naphthenate. Compositions were prepared byusing in parts by weight 100 of polyvinyl chloride: 50 of dioctylphthalate, i. e., bis-(2-ethylhexyl) phthalate, and 2 of stabilizerindicated in the table. The composition were prepared by mixing theresin plasticizer and stabilizer and milling the mixture for 15 minuteson a roll mill with roll temperatures of 132 and 150 C. The sheet fromthe mill was then molded for 2 minutes at 160 C. All the compositionsreported herein were prepared in this manner.

In order to determine the deteriorating effects of heat, samples of thecomposition noted in Table I were exposed for the indicated time at 160C. in a constant temperature oven wherein air circulated.

In order to determine the extent of discoloration, the extinctioncoefiicient of the compositions was measured with the aid of aspectrophotometer, model 11, manufactured by the Coleman ElectricCompany, Inc., Maywood, 11- linois. This instrument has means for generating monochromatic light which is transmit-' ted by means of a narrowslit through the sample whose discoloration is being measured. The lighttransmitted'through the sample falls on a photo tube and the currentproduced therein is measured with the aid of a potentiometer, whichcurrent is a measure of discoloration of the sample as compared to airwhich is colorless. By means of this instrument, numerical values ofdiscoloration are obtained which are known as extinction coefiicients.The extinction coefiicient of air is zero and increased discoloration ofa sample is indicated by increasingly larger extinction coefiicients.Thevalues represented in Table .I were obtained using substantiallymonochromatic light of predominantly 5000 A wave length as were otherextinction coefficients reported herein.

Table I Parts by Weight of Stabilizer per 100 Parts of Polymer Epoxy IV2 0 1 0 l 0 1 Cd N 0 2 1 0 0 0 0 0 0 0 2 1 0 0 0 0 0 0 0 2 l v 0.8 0.70.4 1.8 0.8 0.6 0.5 1.9 1.0 0.5 1.7 1.0 1.3 0.0 2. 5 TD 0. 5 5. 6 1. 46. 8 1.1 1. 2.9 TD 0.5 9.4 1.5 TD 1.6 2. 3.5 TD 0. 6 TD 1. 9 TD 2.0 3.0Hours 5.6 TD 0.8 TD 3.0 TD 3. 9

TD= Sample too discolored to determine extinction cocificlcnt.

The markedly superior and synergistic results obtained with use of thecombination of substances as stabilizer is evident from the aboveresults with compositions subjected to the heat treatment which wassevere for such plastic. Thus, after one-half hour'at 160 C. thecomposition containing the added 2% of the glycidyl ether had anextinction coeflicient of 1.9. Material containing the added 2% ofcadmium naphthenate had an extinction coefiicient of 1.0. On the otherhand, the compositioncontaining an added 1% each of these substances hadan extinction coefiicient of only 0.5 which was less than than with useof either alone. In other words, the extent of discolorationcaused bythe heat was less in the composition containing the combination ofsubstances thanin the compositions containing comparable amounts ofeither substance alone.

The synergistic effect is not unique to aparticular halogen-containingmaterial such as polyvinyl chloride illustrated above. It applies totheother halogen-containing organic material having a molecular weightabove 2000 wherein the halogen atoms are each linked directly to carbonatoms which in turn are linked directly to no other atoms than carbon,hydrogen and oxygen. For example, the synergistic effect is likewiserealized upon using the combination of substances to stabilize thecopolymer containing about 95% vinyl chloride and 5% .vinyl acetatehaving a molecular weight of about 90,000 as illustrated from theresults given in Table II below. In this table, .the compositions weresubjected to the same heat treatment as those for Table I.

In order-to test the stabilizing efiect of the combination of substancesfor compositions subjected tothedeteriorating e'fiects of light,compositions containing the ingredients noted in Table III were preparedandsubjected to light from a carbon are which .isrich in ultravioletradiation for the noted times. The improved stability byuse of thecombination is apparent from the results given in the following table.

Table III Parts by weight With 50 Parts of Diocytl Phthalate I Polyvinylchloride 100 100 100 100 100 100 0 0 0 Copolymer of 95% vinyl chlorideand vinylacetate" O 0 0 0 0 0 100 100 100 100 EpoxyIV. 0 2 1 0 l 1 0 2 01 0 0 2 l I 0 0 0 0 2 1 0 0 0 0 2 1 0 0 0 0 Extinction Coef. after sub-{looting to light radiation 170hrs 0.7P 0.4 1.0 0.4 0.7 0. 12p 03 1.0P0.0 340m 1.2P 0.4 0.7 0.4 0.81 0.3 P=Suriace was pitted.

In the manufacture of many articles from Table V polymers, compositionscontaining the same are subjected to elevated temperatures in a mold inParts by weighoisltabilizcr the absence of contact with heated air. Theper 100 stabilizing effect was tested under such conditions Epoxy IV 0 20 1 0 by placing compositions containing the ingre- 0d Na 0 0 2 1 0 0 SrStearate. 0 0 0 0 2 1 dients noted 1n Table III in a mold at 170 C. forStiffness at start 1,640 1,305 1, 430 1,220 1,450 1,340 20 minutes anddetermimng the extinction 00- g e ga p efficients before and after suchtreatments. ,The mga 6 18 5 8 greater than additive efiect for thecombination 36 31 48 18 17 138 145 49 120 3'3 is again evident from theresults given 1n Table 315 209 49 88 266 74 IV below.

Table IV Parts by Weight With 50 Parts of Dioctyl Phthalate Extinctionflgp ly e oi s Ooef. after 2g 5 viny r min. in mo Polyvinyl Epoxy Cd Sr0 chloride g jg f 1v Naph. 222 Naph at 170 o. acetate 100 0 O 0 0 O 7. 7100 '0 2 0 0 0 3. 9 100 0 O 2 0 O 0.5 100 0 1 1 0 O 0. 4 100 0 0 O 2 02. 3 100 0 1 0 1 0. 0.9 100 0 0 0 0 2 1. 5 100 0 1 0 0 1 0. 7 0 100 O 00 5 1 O 100 2 0 0 0 5 0 100 O 2 O 0 3 9 0 100 1 1 O 0 2 4 0 100 0 0 2 04, 6 0 100 1 0 1 0 2. 4 0 100 o 0 0 2 3. 7 0 100 1 O 0 1 1. 7

Since heat not only tends to discolor l1ydrogen-- containing organicmaterials of high molecular weight, but also adversely afiectsmechanical properties of compositions containing them, it was ofinterest to determine the extent of this type of stabilization gained inthe compositions of the invention for comparison with priorcompositions. The copolymer of 95% vinyl chloride and 5% vinyl acetateplasticized with an added 50% of dioctyl phthalate and containing thestabilizer substances noted in Table V were preparedas described before.Sheets thereof were heat-treated in the air oven at 160 C. for theindicated times and the stiffness in fiexure was determined by ASTMdesignation D 747- 43T. Since the initial stiffness varies somewhat-withthe particular composition, the table records the percentage changewhich resulted from the heat treatment. Therefr'om it will be noted thatthe use of the combination of stabilizing substances gave much superiorresults to use of any single one alone. 1

total stabilizer (glycidyl ether plus strontium or 9:1 of the ether tothe salt, although it is more goreferable to use a more restricted rangeof about Use of larger proportions of the mixture of The proportion ofstabilizing substances employed with the high molecular weighthalogencontaining organic materials may be variedgin; order to meet thestabilizing requirements needed; for the composition. In general, theamount of cadmium salt) is about-0.1'% to 10% of the' halogen-containingsubstance. In special-cases stabilizing substances produces greaterstabilizing effect. In view of the synergism achieved with use of thecombination of glycidyl ether and the metal salt, lesser proportions ofthe combination are needed to produce a greater extent of thestabilization than with use of ether alone. This fact is illustrated bythe results of Table VI below which reports extinction coefficientsobtained in compositions after being subjected to the heat treatment inthe air oven at 160 C. for the noted times. The compositions consist ofpolyvinyl chloride having incorporated therewith 50 parts by weight ofdioctyl phthalate as plasticizer and the indicated parts of stabilizerper 100' parts of polymer. The glycidyl ether designated as Epoxy V wasthat prepared as described in Example V.

Table VI Parts by Weight of Stabilizer per 100 Parts Polymer It will benoted from the foregoing results that an added of strontium naphthenatealone gives a composition having an extinction coeflicient of 8.7 afterheating in air at 160 C. for 3 hours which is substantially the sameextent of discoloration which occurs with the composition containingonly an added 1% each of the glycidyl ether along with the strontiumnaphthenate. Likewise, the use of an added 5% of the glycidyl etheralone gives a composition having an extinction coeflicient of 6.7 afterheating for the same time and temperature which is about the same extentof discoloration occurring with the composition containing about anadded 1.2% each of the'substances. In other words, polyvinyl chloridecontaining an added 1.2% of the glycidyl ether and an added 1.2% of thestrontium naphthenate is stabilized as well or better than polyvinylchloride having incorporated therewith an added 5% of either of thesesubstances alone.

The compositions of the invention may contain in addition to thehalogenated organic material of high molecular weight and thecombination of stabilizing substances, any other material desired suchasplasticizers like dioctyl phthalate,

tricresyl phosphate, chlorinated diphenyland dibutylsebacate, colorants,dyes, pigments and/or fillers. venientto. incorporate the variousmaterials together on a heated roll mill, other conventional andwell-known methods may be used such as by solution wherein all thesubstances are dissolved or mix-ed in a solvent and then the solution issubjected to evaporation of the solvent therefrom.

While the use of the strontium or cadmium. salt in conjunctionvlith theglycidyl ether has been shown to give a synergistic efiect, there may beused in combination with the glycidyl ether any alkaline earth metalsalt of a carboxylic acid, numerous examples-of which have beenenumerated hereinbefore.

I claim as my invention:

1. A composition of matter containing a halogen-containing organicsubstance having a 119- While in general it may be most con.-

lecular weight above 2000 and containing 10% to of halogen in admixturewith 0.1 to 10% of stabilizer therefor consisting essentially of each ofa glycidyl ether having a 1,2-epoxy equivalency greater than one, and acarboxylic acid salt ofa metalfrom the group consisting of cadmium andthe alkaline earth metals, the weight ratio of said ether to said saltbeing from 1:9 to 9:1.

2. A stabilized. composition of matter containing an organic substancehaving a molecular weight above 2000 and containing 10% to 75% ofhalogen in admixture with 0.1% to 10% of heat andlight stabilizertherefor consisting essentially of a glycidyl ether having a 1,2-epoxyequivalency greater than one, and a carboxylic acid salt of cadmium in aweight ratio of 1:9 to 9:1 of said ether to said salt.

3; A stabilized composition of matter containing a polymer of vinylchloride with molecular weight above 2000 and containing at least 10%chlorine in admixture with 1% to 5'% of heat and light stabilizerconsisting essentially of a glycidyl ether of a dihydric phenol having a1,2- epoxy "equivalency greater than one, but not exceeding two,-and astrontium salt of a carboxylic acid containing no more than oneunsaturated carbon-t0-carbon bonding therein, the weight ratio of'saidether to said salt being from 1:9 to 9:1.

4. A stabilized composition of matter containing a polymer of vinylchloride with molecular weight above 2000 and containing at least'10%chlorine in admixture with 1% to 5% of material as sole heat and lightstabilizer therefor consisting essentially of a glycidyl ether having a1,2-epoxy= equivalency greater than one, and a cadmium salt of asaturated monocarboxylic acid, the weight ratio of said ether to saidsalt being from 1:9 to 9:1.

5. A stabilized composition of matter containing polyvinyl chloride withmolecular weight above 2000 in admixture with about 2% of heat and lightstabilizer therefor consisting essentially of about equal parts byweight of glycidyl ether of polyallyl alcohol having a 1,2-epoxyequivalency greater than one, and cadmium naphthenate.

6. A stabilized composition of matter containing a polymer of vinylchloride with up to 15% vinyl acetate in admixture with 1% to 5% of heatand. light stabilizer therefor consisting essentially of a glycidylether of lbis-(e-hydroxyphenyl)-2,2-propane having a 1,2-epoxyequivalency greater than one, but not greater than two, and a strontiumsalt of a saturated monocarboxylic acid of 12 to 20 carbon atoms, theweight ratio of said ether to said salt being from 1:9 to 9:1.

'7. A stabilized composition of matter containing polyvinyl chloridewith molecular weight above 2000 in, admixture with about 2% of heat andlight stabilizer therefor consisting essentially of about equal parts byWeight of a glycidyl ether of bis-(4-hydroxyphenyl)-2,2-propane having a1,2-epoxy equivalency of 1.3 to 2, and strontium naphthenate.

8. A stabilized composition of matter containing polyvinyl chloride withmolecular weight above 2000, in admixture with about 2% of heat and.light stabilizer therefor consisting essentially of about equal parts byweight of a glycidyl ether of bis- (4-hydroxyphenyl) -2,2-propane havinga 1,2-epoxy equivalency of 1.3 to 2,v and a 13 I 14 strontium salt of afatty acid of 12 to 20 carbon atoms. I REFERENCES CITED A stabilizedcomposition of matter oontoin- The following references are of record inthe ing polyvinyl chloride with molecular weight fil f this patent;above 2000 in admixture with about 2% of heat 5 and light stabilizertherefor consisting essen- UNITED STATES PATENTS tially of about equalparts by weight of a glycidyl Number Name Date ether of bis-(l-hydroxyphenyl) -2,2-propane hav- 2,456,216 Richter Dec. 14, 1948 ing a1,2-epoxy equivalency of 1.3 to 2, and stron- 2,462,422 Plambeck Feb.22, 1949 tium stearate.

e DE LOSS E. WINKLER.

1. A COMPOSITION OF MATTER CONTAINING A HALOGEN-CONTAINING ORGANICSUBSTANCE HAVING A MOLECULAR WEIGHT ABOVE 2000 AND CONTAINING 10% TO 75%OF HALOGEN IN ADMIXTURE WITH 0.1 TO 10% OF STABILIZER THEREFORCONSISTING ESSENTIALLY OF EACH OF A GLYCIDYL ETHER HAVING A 1,2-EPOXYEQUIVALENCY GREATER THAN ONE, AND A CARBOXYLIC ACID SALT OF A METAL FROMTHE GROUP CONSISTING OF CADMIUM AND THE ALKALINE EARTH METALS, THEWEIGHT RATIO OF SAID ETHER TO SAID SALT BEING FROM 1:9 TO 9:1.